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WO2000037259A1 - Amelioration de supports d'impression par jet d'encre - Google Patents

Amelioration de supports d'impression par jet d'encre Download PDF

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Publication number
WO2000037259A1
WO2000037259A1 PCT/GB1999/004223 GB9904223W WO0037259A1 WO 2000037259 A1 WO2000037259 A1 WO 2000037259A1 GB 9904223 W GB9904223 W GB 9904223W WO 0037259 A1 WO0037259 A1 WO 0037259A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
element according
top layer
poly
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1999/004223
Other languages
English (en)
Inventor
Julie Baker
John M. Higgins
Malcolm D. Purbrick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to JP2000589351A priority Critical patent/JP2002532309A/ja
Priority to US09/622,462 priority patent/US6534157B1/en
Priority to EP99959600A priority patent/EP1054775B1/fr
Priority to DE69919133T priority patent/DE69919133T2/de
Publication of WO2000037259A1 publication Critical patent/WO2000037259A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • This invention relates to inkjet ink imaging, particularly to inkjet ink image recording elements and to a method for their production.
  • ink droplets are ejected from a nozzle at high speed towards a recording element or medium to produce an image on the medium.
  • the ink droplets, or recording liquid generally comprise a recording agent, such as a dye or pigment, and a large amount of carrier liquid, in particular a solvent.
  • the solvent, or carrier liquid typically is made up of water, an organic material such as a monohydric alcohol or a polyhydric alcohol or a mixed solvent of water and one or more water- miscible solvents such as a monohydric alcohol or a polyhydric alcohol.
  • the recording elements typically comprise a support or a support material having on at least one surface thereof an ink-receiving or image-forming layer.
  • the elements include those intended for reflection viewing, which usually have an opaque support, and those intended for viewing by transmitted light, which usually have a transparent support.
  • the recording element should • Be readily wetted so there is no puddling, i.e. coalescence of adjacent ink dots, which leads to nonuniform density.
  • Image recording elements for inkjet ink images conventionally have a top or "overcoat" layer coated on top of the ink- receiving or imaging- forming layer, the latter also referred to herein as a base layer.
  • An overcoat layer has been used, in particular, when the base layer contains gelatin or a polymer.
  • the overcoat layer can serve various functions, such as to provide physical protection for the underlying layer, reduce tackiness, provide a glossy appearance, offer an ink-receptive surface, carry specific components or allow easier manufacture.
  • the overcoat layers are usually thinner than the underlying base layer typically used for inkjet receivers, such an overcoat layer being commonly about 1 micron ( ⁇ m) thick.
  • the inkjet medium or receiver should dry quickly after the application of the ink. It has been found that by omitting the top or overcoat layer it is sometimes possible to reduce the time taken to dry a printed image (as measured by the density of ink transfe ⁇ ed to a piece of plain paper sandwiched to the printed image immediately after it exits the inkjet printer). However, this is an unsatisfactory way of improving the drying time, for it entails the loss of the advantageous properties that the overcoat layer was intended to provide.
  • the present invention in one of its aspects, provides an image recording element for ink images, especially inkjet ink images, comprising, in the following order, a support, an ink- receptive layer and a top layer, wherein the top layer comprises a polymer that contains both a hydrophilic component and a hydrophobic component, or a mixture of two or more such polymers, the said polymer or polymer mixture being present in the top layer in an amount of from 0.003 to 0.5 g/m 2 .
  • the present invention in another aspect thereof, also provides a method for the preparation of an image recording element for ink images, especially inkjet ink images, which method comprises the steps of forming a precursor element comprising a support and an ink- receptive layer and forming a top layer on the surface of the precursor element remote from the support by applying to the said surface a polymer that contains both a hydrophilic component and a hydrophobic component, or a mixture of two or more such polymers, the polymer or polymer mixture being applied at a rate of from 0.003 to 0.5 g/m 2 .
  • the ink-receptive layer is also referred to herein, for convenience, as a "base layer".
  • base layer the presence of one or more additional layers, for example on the side of the support remote from the base and top layers or situated between the support and the said base layer or situated between the base layer and the top layer, is not precluded.
  • Figure 1 is a graph showing the results of experiments in which the Total Status A Reflection Density was measured for a series of drying times, for a first image-recording element according to the present invention.
  • Figure 2 is a graph showing the results of experiments in which the Total Status A Reflection Density was measured for a series of drying times, for a second image- recording element according to the present invention. In both Figure 1 and Figure 2, the results obtained for a conventional image-recording element are included for comparison purposes.
  • the recording element can be opaque, translucent or transparent.
  • the supports utilised in the recording element of the present invention are not particularly limited and various supports may be employed. Accordingly, plain papers, resin-coated papers, various plastics, for example a polyester-type resin such as poly(ethylene terephthalate), poly(ethylene naphthalate) and polyester diacetate, a polycarbonate-type resin, a fluorine-type resin such as ETFE, metal foil, various glass materials, and the like can be employed as supports.
  • a transparent recording element can be obtained and used as a transparency in an overhead projector.
  • the supports employed in the present invention are preferably self-supporting.
  • self-supporting is meant a support material such as a sheet of film that is capable of independent existence in the absence of a supporting support.
  • the support will be a sheet or sheet-like structure.
  • the thickness of the support will usually be from 12 to 500 ⁇ m, typically from 75 to 300 ⁇ m.
  • the surface of the support may be corona-discharge-treated prior to applying the solvent-absorbing layer or base layer to the support or, alternatively, an under-coating, such as a layer formed from a halogenated phenol or a partially hydrolyzed vinyl chloride-vinyl acetate copolymer can be applied to the surface of the support.
  • the support is a thin sheet or sheet-like structure
  • a coating for example a gel layer
  • the base layer is primarily intended as a sponge layer for the absorption of ink solvent.
  • the base layer is, in general, primarily composed of hydrophilic or porous materials.
  • the base layer may consist of any hydrophilic polymer or combination of polymers with or without additives as is well known in the art. It usually has a thickness of 3 to 20 ⁇ m.
  • the application of one or more additional ink-receptive layers, which may possibly be different in constitution to the base layer, is not, however, precluded.
  • Hydrophilic materials that may be considered for use as or in the base layer include gelatin, acetylated gelatin, phthalated gelatin, oxidised gelatin, chitosan, poly(alkylene oxide), poly(vinyl alcohol), modified poly(vinyl alcohol), sulfonated polyester, partially hydrolysed poly(vinylacetate/vinyl alcohol), poly(acrylic acid), poly(l-vinylpyrrolidone), poly(sodium styrene sulfonate), ⁇ oly(2-acrylamido-2-methane sulfonic acid), and polyacrylamide and mixtures of these materials. Copolymers of these polymers with hydrophobic monomers may also be used.
  • cellulose derivatives include, for example, cellulose derivatives, gum derivatives, chitin and starch.
  • a porous structure may be introduced into the base layer by the addition of ceramic or hard polymeric particulates, by foaming or blowing during coating, or by inducing phase separation in the layer through introduction of nonsolvent.
  • the base layer it is sufficient for the base layer to be hydrophilic, but not porous. This is especially true for photographic quality prints, in which porosity may cause a loss in gloss.
  • rigidity may be imparted to the base layer through incorporation of a second phase comprising one or more materials such as polyesters, poly(methacrylates) and polyvinyl benzene-containing copolymers.
  • the base layer may be pH adjusted to optimise swelling (water capacity), to enhance gloss or to minimise dye migration.
  • the pH of the layer is reduced to 3.5 to improve swelling capacity, thereby reducing ink drying times, and to impart waterfastness.
  • the pH of the image recording layer is raised to 8.5 in order to enhance gloss and reduce bronzing due to surface dye crystallisation.
  • 50%- 100% by weight of the base layer is composed of photographic-grade gelatin, modified such that the pH is far from the isoelectric point of such a gelatin, in order that water uptake may be maximised.
  • the remainder (if any) of the layer may consist of a polymer or inorganic material compatible with said gelatin and which does not adversely impact functional properties.
  • a mordant may be added in small quantities (2%-10% by weight of the base layer) to further improve waterfastness.
  • Useful mordants are disclosed in U.S. Patent 5,474,843, the teaching in which is incorporated herein by reference.
  • the top layer comprises, for example consists essentially of, one or more polymers that contain both a hydrophobic component or constituent and a hydrophilic component or constituent.
  • the polymer backbone itself, or a part thereof may constitute one such component, in particular a hydrophobic component.
  • preferred polymers contain the following functionalities, namely both hydrophilic substituents and hydrophobic substituents. In general, such substituents will be pendant from, or otherwise incorporated into, the polymer backbone.
  • Various polymers will confer different degrees of hydrophobic and hydrophilic character to the overcoat layer and hence the person skilled in the art will be able to select a particular polymer to fulfil particular requirements.
  • Suitable polymers include those containing carboxylic acid groups and/or esters thereof and/or salts thereof.
  • the top or overcoat layer comprises at least one acrylic polymer, especially at least one polymer selected from the group consisting of (i) polymers of acrylic acid, methacrylic acid, an acrylic acid ester or a methacrylic acid ester, (ii) copolymers containing units derived from at least one of acrylic acid, methacrylic acid, an acrylic acid ester and a methacrylic acid ester, and (iii) salts of the aforesaid polymers (i) and copolymers (ii).
  • Preferred acrylic and methacrylic acid esters are the alkyl esters, especially the C C 6 alkyl esters, more especially the methyl or ethyl esters.
  • Suitable salts include the alkali metal salts, for example the sodium or potassium salts.
  • the copolymers may consist essentially of units derived from two or more of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters. However, other suitable copolymers comprise units derived from at least one of the said acids and esters, together with units derived from one or more other monomeric species, e.g. ethylene glycol, ethylene oxide, a carboxylic acid, for example maleic acid, or a (meth)acrylic acid amide.
  • Various types of copolymer may come into consideration, including block copolymers and graft copolymers. Crosslinking of the polymers and copolymers may also come into consideration.
  • the methyl methacrylate group is more hydrophobic than the etherified group, which latter therefore constitutes the hydrophilic component.
  • the acrylic moiety is the more hydrophobic, the maleic moiety therefore constituting the hydrophilic component.
  • poly(methyl methacrylate) the polymer backbone is regarded as the hydrophobic component and therefore the methacrylic ester group is regarded as the hydrophilic component.
  • the constituent polymer or mixture of polymers is generally applied at a rate of from 0.003 to 0.5 g/m 2 .
  • the laydown of the polymer or polymer mixture is in the range of from 0.004 to 0.2 g/m 2 , more preferably from 0.005 to 0.1 g/m 2 .
  • a laydown of 1 g/m 2 gives rise to a thickness of l ⁇ m, assuming uniform application.
  • topcoat in accordance with the present invention results in a discontinuous top layer.
  • the top layer will typically cover 50 to 75% of the surface area, as measured by atomic force microscopy.
  • the discontinuities may be randomly distributed.
  • amphiphilic "overcoat” polymers will be templated (or “induced” or “constrained”) by the conditions under which they are coated and by the nature of the underlying substrate, so that the conformation assumed by the "overcoat” polymer(s) will lead to a predominance of hydrophobic substituents at the top surface of the inkjet element or medium, with hydrophilic groups tending to be drawn towards the underlying (substrate or base) layer. It is believed, however, that, notwithstanding the presentation of the hydrophobic domains at the surface, the discontinuities in the top layer allow the inkjet ink to migrate rapidly to the hydrophilic domains with consequent improvements in drying time.
  • the image recording element may come in contact with other image recording articles or the drive or transport mechanisms of the image recording devices for which its use is intended, additives such as surfactants, lubricants, matte particles and the like may be optionally added to the element to the extent that they do not unduly degrade properties of interest.
  • the layers described above, including the base layer and the top layer, may be coated by conventional coating means onto a support material, e.g. a transparent or opaque support material commonly used in this art.
  • Coating methods may include, but are not limited to, wound wire rod coating, slot coating, slide hopper coating, gravure, curtain coating and the like. Some of these methods allow for simultaneous coatings of both layers, which is preferred from a manufacturing economic perspective.
  • the inks used to image the recording elements according to the present invention are well- known inks.
  • the ink compositions used in ink-jet printing typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, and the like.
  • the solvent or carrier liquid can be comprised solely of water or can be predominantly water mixed with one or more other, water-miscible, solvents such as polyhydric alcohols, although inks in which organic materials such as polyhydric alcohols are the predominant carrier or solvent liquid also may be used. Particularly useful are mixed solvents of water and polyhydric alcohols.
  • the dyes used in such compositions are typically water-soluble direct or acid type dyes.
  • Such liquid compositions have been described extensively in the prior art including, for example, U.S. Patent No. 4,381,946, No. 4,239,543 and No. 4,781,758, the teaching in each of which is incorporated herein by reference
  • Pen plotters operate by writing directly on the surface of a recording medium using a pen consisting of a bundle of capillary tubes in contact with an ink reservoir.
  • the image recording elements according to the present invention exhibit excellent drying times in comparison with conventional elements containing thicker top layers. Indeed, in certain embodiments of the present invention the improvements in drying time exceed those obtained by simply omitting the top or "overcoat” layer.
  • the recording elements according to the present invention can exhibit excellent drying times even under conditions of high humidity. Moreover, the improvements in drying time may be obtained whilst retaining the usual desirable properties offered by the use of a top or "overcoat” layer.
  • the present invention is illustrated in and by the following Example.
  • the ink-absorbing layer included 848 mg/m 2 of a catiomc latex polymer (a polymer of (m- and p- chloromethyl) ethenyl benzene and 2-methyl-2-propenoic acid 1,2-ethanediylester, quaternized with N,N- dimethylmethanamine) which acts as a mordant and also 129.16 mg/m of polymeric matte (limited coalescence polystyrene beads, 20 ⁇ m).
  • a catiomc latex polymer a polymer of (m- and p- chloromethyl) ethenyl benzene and 2-methyl-2-propenoic acid 1,2-ethanediylester, quaternized with N,N- dimethylmethanamine
  • Table 1 hereinafter shows the results for the density of ink transferred to the plain paper after various time intervals after the imaged paper had exited the printer. The results are shown for samples A to H, in comparison with the control, wherein the image-recording element was Kodak (trade mark) Inkjet Photographic Quality Paper Photo Weight.
  • Table 1 show that all of the polymeric overcoats gave rise to an improvement in dry time, as indicated by the reduced density of ink transferred to the plain paper. Further tests were carried out by measuring the total status A reflection density for samples of inkjet image-recording elements prepared in the same manner as samples B and D above, over a range of drying times. Use was made of an HP PhotoSmart Printer and the tests were conducted at 80% RH. Similar tests were carried out, by way of comparison, on a conventional image-recording element for inkjet ink images, the conventional elements having a top layer comprising cellulose compounds coated at a rate of 1 g/m 2 . The results are shown in Figures 1 (Polymer B) and 2 (Polymer D).
  • phase imaging maps the phase of the cantilever oscillation during the tapping mode scan and detects variations in composition, adhesion, friction and viscoelasticity. It is possible to evaluate the extent of the coverage in the phase mode in terms of the bearing area measurements calculated from the phase mode images.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne un élément d'impression d'images à l'encre par jet d'encre, l'élément comprenant un support, une couche réceptrice d'encre et une couche supérieure, la couche supérieure comprenant un polymère qui contient un composant hydrophile et un composant hydrophobe, ou un mélange de deux ou de plusieurs polymères, la quantité du polymère ou du mélange de polymères dans la couche supérieure étant comprise entre 0,003 et 0,5 g/m2. La couche supérieure comprend de préférence un polymère contenant des substituants hydrophiles et des substituants hydrophobes, comme par exemple un polymère sélectionné dans le groupe formé par les polymères et copolymères d'acide acrylique, d'acide méthacrylique, d'esters d'acide acrylique ou d'esters d'acide méthacrylique, ou un sel de ce polymère ou copolymère. La couche de base, pouvant contenir de la gélatine, possède de préférence une épaisseur comprise entre 3 et 20 νm. Le support peut être un support classique, par exemple une feuille de papier. L'invention permet d'améliorer le temps de séchage des images imprimées par jet d'encre, même dans des conditions d'humidité élevée.
PCT/GB1999/004223 1998-12-19 1999-12-14 Amelioration de supports d'impression par jet d'encre Ceased WO2000037259A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2000589351A JP2002532309A (ja) 1998-12-19 1999-12-14 インクジェット媒体における改良
US09/622,462 US6534157B1 (en) 1998-12-19 1999-12-14 Ink-jet media
EP99959600A EP1054775B1 (fr) 1998-12-19 1999-12-14 Amelioration de supports d'impression par jet d'encre
DE69919133T DE69919133T2 (de) 1998-12-19 1999-12-14 Verbesserungen an tintenstrahlmedien

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9827980.5A GB9827980D0 (en) 1998-12-19 1998-12-19 Recording material for inkjet printing
GB9827980.5 1998-12-19

Publications (1)

Publication Number Publication Date
WO2000037259A1 true WO2000037259A1 (fr) 2000-06-29

Family

ID=10844547

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/004223 Ceased WO2000037259A1 (fr) 1998-12-19 1999-12-14 Amelioration de supports d'impression par jet d'encre

Country Status (6)

Country Link
US (1) US6534157B1 (fr)
EP (1) EP1054775B1 (fr)
JP (1) JP2002532309A (fr)
DE (1) DE69919133T2 (fr)
GB (1) GB9827980D0 (fr)
WO (1) WO2000037259A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1275516A1 (fr) 2001-07-10 2003-01-15 Eastman Kodak Company Matériaux pour l'enregistrement par jet d'encre et méthode pour leur fabrication
WO2003037641A2 (fr) 2001-11-02 2003-05-08 Ciba Specialty Chemicals Holding Inc. Support d'enregistrement a jet d'encre
WO2003054029A1 (fr) * 2001-12-21 2003-07-03 Ciba Specialty Chemicals Holding Inc. Copolymeres de poly(vinyl alcool)-co-poly(n-vinyl formamide)
US7572843B2 (en) 2001-12-21 2009-08-11 Ciba Specialty Chemicals Corporation Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties

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ITSV20020022A1 (it) * 2002-05-21 2003-11-21 Ferrania Spa Sistema di stampa a getto di inchiostro
ITSV20020023A1 (it) * 2002-05-21 2003-11-21 Ferrania Spa Foglio recettore di inchiostro
MY144216A (en) * 2003-07-10 2011-08-15 Ciba Holding Inc Polycondensates as dyeing promoters for hydrophobic polymer articles
MXPA06000374A (es) * 2003-07-10 2006-03-17 Ciba Sc Holding Ag Medio de grabacion por inyeccion de tinta.
DE10361247A1 (de) * 2003-12-22 2005-07-28 Deutsche Gelatine-Fabriken Stoess Ag Chitosan und dessen Verwendung als Farbfixierungsmittel in Ink-Jet-Aufzeichnungsmaterialien
US7361399B2 (en) * 2004-05-24 2008-04-22 International Paper Company Gloss coated multifunctional printing paper
FI123391B (fi) * 2005-12-01 2013-03-28 Aalto Korkeakoulusaeaetioe Menetelmä paperin tai kartongin painopinnan modifioimiseksi
US20080039549A1 (en) * 2006-06-30 2008-02-14 Jun Li Two-Part Printing System with Acrylic-Based Polymers
DE102006060340B4 (de) * 2006-12-13 2012-12-13 Leibniz-Institut Für Polymerforschung Dresden E.V. Verwendung einer dauerhaften Beschichtung von Metall- oder Glasoberflächen zurBe- und/oder Verhinderung des Vereisens
US9296244B2 (en) 2008-09-26 2016-03-29 International Paper Company Composition suitable for multifunctional printing and recording sheet containing same

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1275516A1 (fr) 2001-07-10 2003-01-15 Eastman Kodak Company Matériaux pour l'enregistrement par jet d'encre et méthode pour leur fabrication
WO2003037641A2 (fr) 2001-11-02 2003-05-08 Ciba Specialty Chemicals Holding Inc. Support d'enregistrement a jet d'encre
US7544401B2 (en) 2001-11-02 2009-06-09 Ciba Specialty Chemicals Corporation Ink jet recording medium
WO2003054029A1 (fr) * 2001-12-21 2003-07-03 Ciba Specialty Chemicals Holding Inc. Copolymeres de poly(vinyl alcool)-co-poly(n-vinyl formamide)
CN1332989C (zh) * 2001-12-21 2007-08-22 西巴特殊化学品控股有限公司 聚乙烯醇－共－聚(n－乙烯基甲酰胺)共聚物
US7572843B2 (en) 2001-12-21 2009-08-11 Ciba Specialty Chemicals Corporation Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties

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DE69919133D1 (de) 2004-09-09
JP2002532309A (ja) 2002-10-02
US6534157B1 (en) 2003-03-18
EP1054775B1 (fr) 2004-08-04
DE69919133T2 (de) 2005-08-11
GB9827980D0 (en) 1999-02-10
EP1054775A1 (fr) 2000-11-29

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